EP1348693A1 - Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen - Google Patents
Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen Download PDFInfo
- Publication number
- EP1348693A1 EP1348693A1 EP02007068A EP02007068A EP1348693A1 EP 1348693 A1 EP1348693 A1 EP 1348693A1 EP 02007068 A EP02007068 A EP 02007068A EP 02007068 A EP02007068 A EP 02007068A EP 1348693 A1 EP1348693 A1 EP 1348693A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sodium salt
- naphthoquinone
- diazo
- diphosgene
- triphosgene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
Definitions
- the present invention relates to a process for the preparation of diazonaphthoquinonesulfonylchlorides, useful intermediates in electronic industry and dye industry.
- This research pertains to a method of preparation of diazonaphthoquinonesulfonylchlorides having formula 1-3 from corresponding diazonaphthoquinonesulfonic acid or its sodium salt, using diphosgene or triphosgene.
- Another method involves use of thionylchloride with dimethylformamide as catalyst with the corresponding diazonaphthoquinonesulfonic acid or its salt. This method also suffers the disadvantages like heating the reaction mixture, use of excess thionylchloride and evolution of sulfurdioxide and hydrogenchloride gases (CA, vol. 96, 34766b, Khim. Process, year 1981, p505 (Russ)).
- Another method involves use of chlorosulfonic acid in combination with thionylchloride along with the corresponding diazonaphthoquinonesulfonic acid or its salt.
- the main disadvantages are the same as mentioned above (CA, vol. 105, 208620w, Ger (East) 272,511, year 1985 and DD 234, 000, year 1986; CA vol. 112, 178384x, Ger (East) DD 269,846, year 1989, Ger (East) 312,180, year 1988; CA, vol. 124, 302642u, JP 08,27,098, year 1996; CA, vol. 125, 170873d, RO 104,624, year 1994).
- Yet another method involves is the use of phosgene (toxic gas) with the corresponding diazonaphthoquinonesulfonic acid or its salt.
- This method has the optimum temperature conditions but the greatest disadvantage is the use of toxic phosgene gas (CA, vol. 102, 113031d, JP 59,196,860, year 1984; CA, vol. 105, 60439w, EP 178,356, year 1986).
- the present invention describes an altogether new process for the preparation of diazonaphthoquinonesulfonylchlorides by reacting the corresponding diazonaphthoquinone sulfonic acid or its salt either with diphosgene or triphosgene in presence of triethylamine base in dichloromethane solvent.
- Various solvents like, chloroform, 1,2-dichloroethane, benzene, toluene, acetonitrile, benzonitrile, nitrobenzene and others are also used.
- Organic bases like tributylamine, pyridine, tripropylamine, N,N-dimethylaniline, N,N-diethylamine and other bases are also employed.
- Dichloromethane as solvent and triethylamine as organic base were preferred.
- the temperature of the reaction was varied over -50 to +5°C and -40°C is the preferred temperature condition.
- the base is found to be essential for the reaction to be conducted and without the organic base there is no reaction occurs.
- the 2 mole equivalent ratio of base is the right combination found.
- the work up procedure and isolation of the product diazonaphthoquinonesulfonylchloride is very simple and rapid. After the reaction the organic base and the solvent can be recovered. After the isolation of the product, the remaining filtrate contains the unreacted diazonaphthoquinonesulfonic acid as judged by the UV-Visible absorption data.
- the products were characterized by the spectral data.
- the present invention provides a process for the preparation of diazonaphthoquinonesulfonylchlorides of formula 1-3, using diphosgene or triphosgene which comprises reacting diazonaphthoquinonesulfonicacid sodium salt with an organic base in a molar ratio ranging between 1: 1.5 - 1: 2.5 in an organic solvent in the presence of diphosgene or triphosgene in a molar ratio of diazonaphthoquinonesulfonicacid sodium salt to diphosgene or triphosgene in the range of 1:1-1:1.5 ,at a temperature ranging from -50 °C to 5°C, for a period ranging from 40-90 min, subsequently increasing the temperature to 20-25°C, removing the solvent and base from the above said reaction mixture under vacuum to obtain the yellow powder product and re-precipitating the desired product in ice water.
- the organic base used is selected from the group consisting of triehylamine, tributylamine, pyridine, tripropylamine, N,N-dimethylaniline and N,N-diethylamine.
- organic base used is triehylamine.
- the organic solvent used is selected from the group consisting of chloroform, 1,2-dichloroethane, benzene, toluene, acetonitrile, benzonitrile, nitrobenzene and dichloromethane.
- organic solvent used is dichloromethane.
- the molar ratio of diazonaphthoquinonesulfonicacid sodium salt to organic base used is 1:2.
- the molar ratio of diazonaphthoquinone sulfonicacid sodium salt to triphosgene or diphosgene used is 1:1.
- the diazonaphthoquinonesulfonicacid sodium salt used is selected from 2-Diazo-1-naphthoquinone-4-sulfonic acid sodium salt, 2-Diazo-1-naphthoquinone-5-sulfonic acid sodium salt and 1-Diazo-2-naphthoquinone-4-sulfonic acid sodium salt.
- the diazonaphthoquinonesulfonul chloride obtained is selected from 2-Diazo-1-naphthoquinone-4-chloride of formula 1, 2-Diazo-1-naphthoquinone-5-sulfonulchloride of formula 2, and 1-Diazo-2-naphthoquinone-4-sulfonulchloridesulfonulchloride of formula 3.
- 2-Diazo-1-naphthoquinone-4-sulfonic acid sodium salt (2.72g; 0.01mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
- triethylamine (2.02g; 0.02mol) to the above solution and maintained the temperature at -50°C.
- diphosgene (2.18g; 0.011mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20min.
- the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
- the remaining yellow powder was poured into ice water after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
- the dried 2-diazo-1-naphthoquinone-4-sulfonylchloride weight was 2.14g(0.0080mol) yield 80% m.p 138 -140°C.
- the 2-diazo-1-naphthoquinone-4-sulfonylchloride was characterized by UV-Visible absorption, 1 H-nmr and Mass spectrometry.
- 2-Diazo-1-naphthoquinone-4-sulfonic acid sodium salt (10g; 0.037mol) was taken into 90 ml of dichloromethane and cooled to -50°C.
- triethylamine (7.4g; 0.073mol) to the above solution and maintained the temperature at -50°C.
- the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
- the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
- the dried 2-diazo-1-naphthoquinone-4-sulfonylchloride weight was 7.93g (0.0296mol) yield 80%.
- 2-Diazo-1-naphthoquinone-5-sulfonic acid sodium salt (2.72g; 0.01mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
- triethylamine (2.02g; 0.02mol) to the above solution and maintained the temperature at -50°C.
- diphosgene (2.18g; 0.011mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20min.
- the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
- the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
- the dried 2-diazo-1-naphthoquinone-5-sulfonylchloride weight was 2.14g(0.0080mol) yield 80% mp 135-138°C.
- the 2-diazo-1-naphthoquinone-5-sulfonylchloride was characterized by UV-Visible absorption, 1 H-nmr and Mass spectrometry.
- 2-Diazo-1-naphthoquinone-5-sulfonic acid sodium salt (10g; 0.037mol) was taken into 90ml of dichloromethane and cooled to -50°C.
- triethylamine (7.4g; 0.073mol) to the above solution and maintained the temperature at -50°C.
- diphosgene (7.35g; 0.037mol) in 15ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 30min.
- the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
- the remaining yellow powder was poured into ice water after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
- the dried 2-diazo-1-naphthoquinone-5-sulfonylchloride weight was 7.93g(0.0296mol) yield 80%.
- Example 5 1-Diazo-2-naphthoquinone-4-sulfonic acid sodium salt (2.72g; 0.01mol) was taken into 25 ml of dichloromethane and cooled to -50°C. Added triethylamine (2.02g; 0.02mol) to the above solution and maintained the temperature at -50°C. Then added diphosgene (2.18g; 0.011mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20 min. The reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
- the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
- the dried 1-diazo-2-naphthoquinone-4-sulfonylchloride weight was 2.14 g(0.0080mol) yield 80%, m.p 138 -140°C.
- the 1-diazo-2-naphthoquinone-4-sulfonylchloride was characterized by UV-Visible absorption, 1 H-nmr and Mass spectrometry.
- 2-Diazo-1-naphthoquinone-4-sulfonic acid sodium salt (2.72g; 0.01mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
- triethylamine (2.02g; 0.02 mol) to the above solution and maintained the temperature at -50°C.
- triphosgene (3.2g; 0.011 mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20 min.
- the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine were removed under vacuum.
- the remaining yellow powder was poured into ice water, after 5min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
- the dried 2-diazo-1-naphthoquinone-4-sulfonylchloride weight was 2.14 g (0.0080mol) yield 80%.
- 2-Diazo-1-naphthoquinone-5-sulfonic acid sodium salt (2.72g; 0.01 mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
- triethylamine (2.02g; 0.02 mol) to the above solution and maintained the temperature at -50°C.
- triphosgene (3.2g; 0.011 mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20 min.
- the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine were removed under vacuum.
- the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
- the dried 2-diazo-1-naphthoquinone-5-sulfonylchloride weight was 2.14 g (0.0080mol) yield 80%.
- 1-Diazo-2-naphthoquinone-4-sulfonic acid sodium salt (2.72g; 0.01 mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
- triethylamine (2.02g; 0.02 mol) to the above solution and maintained the temperature -50°C.
- triphosgene (3.2g; 0.011 mol) in 15 ml dichloromethane very slowly and maintaining the temperature -50°C with stirring over a period of 20 min.
- the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
- the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
- the dried 1-diazo-2-naphthoquinone-4-sulfonylchloride weight was 2.14 g (0.0080mol) yield 80%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02007068A EP1348693B1 (de) | 2002-03-27 | 2002-03-27 | Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen |
DE60222376T DE60222376T2 (de) | 2002-03-27 | 2002-03-27 | Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02007068A EP1348693B1 (de) | 2002-03-27 | 2002-03-27 | Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1348693A1 true EP1348693A1 (de) | 2003-10-01 |
EP1348693B1 EP1348693B1 (de) | 2007-09-12 |
Family
ID=27798817
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02007068A Expired - Lifetime EP1348693B1 (de) | 2002-03-27 | 2002-03-27 | Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen |
Country Status (2)
Country | Link |
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EP (1) | EP1348693B1 (de) |
DE (1) | DE60222376T2 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007026374A1 (en) * | 2005-09-01 | 2007-03-08 | Council Of Scientific And Industrial Research | A single pot process for the preparation of diazonaphthoquinonesulfonyl ester |
EP2581363A1 (de) * | 2011-10-14 | 2013-04-17 | Lonza Ltd | Flüssiges Phosgenierungsreagenz |
CN105693564A (zh) * | 2016-04-02 | 2016-06-22 | 田菱精细化工(大连)有限公司 | 一种萘醌磺酰氯的合成方法 |
CN105753743A (zh) * | 2016-04-02 | 2016-07-13 | 田菱精细化工(大连)有限公司 | 一种合成萘醌磺酰氯的方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102408364B (zh) * | 2010-09-26 | 2014-11-12 | 中化蓝天集团有限公司 | 一种制备对甲苯磺酰氯的方法 |
-
2002
- 2002-03-27 EP EP02007068A patent/EP1348693B1/de not_active Expired - Lifetime
- 2002-03-27 DE DE60222376T patent/DE60222376T2/de not_active Expired - Lifetime
Non-Patent Citations (2)
Title |
---|
E. SAUER, ET AL.: "Sulfochlorierung von 1,2-Naphthochinondiazid-(2) mit Chlorsulfonsäure", JOURNAL FÜR PRAKTISCHE CHEMIE, vol. 333, no. 3, 1991, Leipzig, DE, pages 467 - 473, XP000925654, ISSN: 0021-8383 * |
R.C. REYNOLDS, ET AL.: "Synthesis of thymidine dimers containig internucleoside sulphonate and sulphonamide linkages", JOURNAL OF ORGANIC CHEMISTRY, vol. 57, no. 11, 22 May 1992 (1992-05-22), American Chemical Society, Washington, DC, US, pages 2983 - 2985, XP002211505, ISSN: 0022-3263 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007026374A1 (en) * | 2005-09-01 | 2007-03-08 | Council Of Scientific And Industrial Research | A single pot process for the preparation of diazonaphthoquinonesulfonyl ester |
JP2009507013A (ja) * | 2005-09-01 | 2009-02-19 | カウンシル・オブ・サイエンティフィック・アンド・インダストリアル・リサーチ | ジアゾナフトキノンスルホニルエステルの製造のためのシングルポットプロセス |
EP2581363A1 (de) * | 2011-10-14 | 2013-04-17 | Lonza Ltd | Flüssiges Phosgenierungsreagenz |
CN105693564A (zh) * | 2016-04-02 | 2016-06-22 | 田菱精细化工(大连)有限公司 | 一种萘醌磺酰氯的合成方法 |
CN105753743A (zh) * | 2016-04-02 | 2016-07-13 | 田菱精细化工(大连)有限公司 | 一种合成萘醌磺酰氯的方法 |
Also Published As
Publication number | Publication date |
---|---|
DE60222376T2 (de) | 2008-05-29 |
DE60222376D1 (de) | 2007-10-25 |
EP1348693B1 (de) | 2007-09-12 |
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